Bituminous compositions containing methylol phenol derivatives



United dtates Patent ration of Delaware No Drawing. Original application May 12, 1960, Ser- No. 28,514. Divided and this application Apr. 10,

1961, Ser. No. 101,629

16 Claims.

This application is a division of our copending application Serial No. 28,514, filed May 12, 1960, which latter application is a continuation-in-part of our copending application Serial No. 730,510, filed April 24, 1958, now abandoned. See also our copending application Serial No. 804,086, filed April 6, 1959, now abandoned, which is a division of Serial No. 730,510. This invention relates to bituminous compositions containing (1) oxyalkylated, (2) acylated, (3) oxyalkylated then acylated, (4) acylated thenoxyalkylated, and (5) acylated, then oxyalkylated and then acylated, monomeric polyaminomethyl phenols. These substituted phenols are produced by a process which is characterized by reacting a preformed methylol phenol (i.e. formed prior to the addition of the polyamine) with at least one mole of a secondary polyamine per equivalent of methylol group on the phenol, in the absence of an extraneous catalyst (in the case of an aqueous reaction mixture, the pH of the reaction mixture being determined solely by the methylol phenol and the secondary polyamine), until about one mole of Water per equivalent of methylol group is removed; and then reacting this product with (1) an oxyalkylating agent, (2) an acylating agent, (3) an oxyalkylating agent then an acylating agent, (4) an acylating agent then an oxyalkylating agent or (5) an acylating agent then an oxyalkylating agent and then an acylating agent.

The reasons for the unexpected monomeric form and properties of the polyaminomethyl phenol are not understood. However, we have discovered that when (l) A preformed methylolphenol (i.e. for-med prior to the addition of the polyamine) employed as a starting material is reacted with (2) A polyamine which contains at least one secondary amino group (3) In amounts of at least one mole of secondary polyamine per equivalent of methylol group on the phenol,

(4) In the absence of an extraneous catalyst, until (5) About one mole of water per equivalent of methylol group is removed, then a monomeric polyaminornethyl phenol is produced which is capable of being oxyalkylated, acylated, oxyalkylated then acylated, or acylated then oxyalkylated, or acylated, then oxyalkylated and then 'acylated to provide the superior products employed in the compositions of this invention. All of the above five conditions are critical for the production of these monomeric po-lya-minomethyl phenols.

In contrast, it the methylol phenol is not preformed but is formed in the presence of the polyamine, or the preformed methylol phenol is condensed with the polyamine in the presence of an extraneous catalyst, either acidic or basic, for example, basic or alkaline materials such as NaOH, Ca(OH) Na CO sodium methylate, etc., a polymeric product is formed. Thus, if an alkali metal phenate is employed in place of the free phenol, or even if a lesser quantity of alkali metal is present than is required to form the phenate, a polymeric product is formed. Where a polyamine containing only primary amino groups and no secondary amino groups is reacted with a methylol phenol, a polymeric product is also produced. Similarly, where less than one mole of secondary 3,005,190 Patented July 2, 1963 ice 2 amine is reacted per equivalent of methylol group, a polymeric product is also formed.

In general, the monomeric polyaminomethyl phenols are prepared by condensing the methylol phenol with the secondary amine as disclosed above, said condensation being conducted at a temperature sufficiently high to eliminate water but below the pyrolytic point of the reactants and product, for example, at to 200 C., but preferably at to C. During the course of the condensation water can be removed by any suitable means, for example, by use of an azeotroping agent, reduced pressure, combinations thereof, etc. Measuring the water given ofi during the reaction is a convenient method of judging completion of the reaction.

The classes oi methylol phenols employed in the condensation are as follows:

Monophenols: A phenol containing 1, 2 or 3 methylol groups in the ortho or para position (i.e. the 2, 4, 6 positions), the remaining positions on the ring containing hydrogen or groups which do not interfere with the polyamine-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, and alk-oxy, etc., groups, and having :but one nuclear linked hydroxyl group.

Diphenols: One type is a diphenol containing two hydroxybenzene radicals directly joined together through the ortho or para (i.e. 2, 4, or 6) position with a bond joining the carbon of one ring with the carbon of the other ring, each 'hydroxyhenzene radical containing 1 to 2 methylol groups in the 2, 4 or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyamine-methyl- 'ol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc, groups, and having but two nuclem linked hydroxyl groups.

, A second type is a diphenol containing two hydroxyenzene radicals joined together through the ortho or para (i.e. 2, 4, or 6 position) with a bridge joining the carbon of one ring to a carbon of the other ring, said bri ge being, for example, alkylene, alkylidene, oxygen, carbonyl, sulfur, sulfox-ide and sulfone, etc, each "nydroxyhenzene radical containing 1 to 2 methylol groups in the 2, 4, or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interefere with the polyaminomethylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc, groups, and having but two nuclear linked hydroxyl groups.

The secondary polyamines employed in producing the condensate are illustrated by the following general formula:

where at least one of the Rs contains an amino group and the Rs contain alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkaryl radicals, and the corresponding radicals containing heterocyclic rachcals, hydroxy radicals, etc. The Rs may also be joined together to form heterocyclic polyamines. The preferred classes of polyamines are the alkylene polyamines, the hydroxylated 'alkylene polyamines, branched polyamines containing at least three primary amino groups, and polyamines containing cyclic amidine groups. The only limitation is that there shall be present in the polyamine at least one secondary amino group which is not bonded directly to a negative radical which reduces the basicity of the amine, such as a phenyl group.

An unusual feature of the products employed in the compositions of the present invention is the discovery that methylol phenols react more readily under the herein specified conditions with secondary amino groups than I 3 with primary amino groups. Thus, where both primary and secondary amino groups are present in the same molecule, reaction occurs more readily with the secondary amino group. However, where the polyamine contains only primary amino groups, the product formed under reaction conditions as mentioned above is an insoluble resin. In contrast, where the same number of primary amino groups are present on the amine in addition to at least one secondary amino group, reaction occurs predominantly with the secondary amino group to form nonresinous derivatives. Thus, where trimethylol phenol is reacted with ethylene diamine, an insoluble resinous composition is produced. However, where diethylene triamine, a compound having just as many primary amino groups as ethylene diamine, is reacted, according to this invention a non-res'mous product is unexpectedly formed.

The term monomeric as employed in the specification and claims refers to a polyaminomethylphenol containing within the molecular unit one aromatic unit corresponding to the aromatic unit derived from the starting methylol phenol and one polyamine unit for each methylol group originally in the phenol. This is in contrast to a polymeric or resinous polyaminomethyl phenol containing within the molecular unit more than one aromatic unit and/or more than one polyamino unit for each methylol group.

The monomeric products produced by the condensation of the methylol phenol and the secondary amine may be illustrated by the following idealized formula:

where A is the aromatic unit corresponding to that of the methylol reactant, and the remainder of the molecule is the polyaminomethyl radical, one for each of the original methylol groups.

This condensation reaction may be followed by oxyalkylation in the conventional manner, for example, by means of an alpha-beta alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, a higher alkylene oxide, styrene oxide, glycide, methylglycide, etc., or combinations thereof. Depending on the particular application desired, one may combine a large proportion of alkylene oxide, particularly ethylene oxide, propylene oxide, a combination or alternate additions or propylene oxide and ethylene oxide, or smaller proportions thereof in relation to the methylol phenol-amine condensation product. Thus, the molar ratio of alkylene oxide to amine condensate can range within wide limits, for example, from a 1:1 mole ratio to a ratio of 100011, or higher, but preferably 1 to 200. By proper control, desired hydrophilic or hydrophobic properties are imparted to the composition. As is well known, oxyalkylation reactions are conducted under a wide variety of conditions, at low or high pressures, at low or high temperatures, in the presence or absence of catalyst, solvent, etc. For instance oxyalkylation reactions can be carried out at temperatures of from 80200 C., and pressures of from to 200 p.s.i., and times of from min. to several days. Preferably oxyalkylation reactions are carried out at 80 to 120 C. and 10' to 30 psi. For conditions of oxyalkylation reactions see US. Patent 2,792,369 and other patents mentioned therein.

As in the amine condensation, acylation is conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactantsand the reaction products. In general, the reaction is carried out at a temperature of from 140'" to 280 C., but preferably at 140 to 200 C. In acylating, one should control the reaction so that the phenolic hydroxyls are not acylated. Because acyl halides and anhydrides are capable of reacting with phenolic hydroxyls, this type of acylation should be avoided. It should be realized that either oxyalkylation or acylation can be employed alone or each alternately, either one preceding the other. In addition, the amine condensate can be acylated, then oxyalkylated and then reacylated. The amount of acylation agent reacted will depend on reactive groups or the compounds and properties desired in the final product, for example, the molar ratios of acylation agent to amine condensate canrange from 1 to 15, or higher, but preferably 1 to 4.

Where the above amine condensates are treated with alkylene oxides, the product formed will depend on many factors, for example, whether the amine employed is hydroxylated, etc; Where the amines employed are nonhydroxylated, the amine condensate isat least susceptible to oxyalkylation through the phenolic hydroxyl radical.

Although the polyamine is non-hydroxylated, it may have' one or more primary or secondary amino groups which may be oxyalkylated, for example, in the case of tetra ethylene pentamine. Such groups may or may not be susceptible to oxyalkylation for reasons which are obscure.

Where the non-hydroxylated amine contains a pinrality of secondary amino groups, wherein one or more is susceptible to oxyalkylation, or primary amino groups, oxyalkylation may occur in those positions. Thus, in the case of the non-hydroxylated polyamines oxyalkylation may take place not only at the phenolic hydroxyl group but also at one or more of the available amino groups. Where the amine condensate is hydroxyalkylated, this latter group furnishes an additional position of oxyalkylation susceptibility. I

The product formed in acylation will vary with the particular polyaminomethyl phenol employed. It may be an ester or an amide depending on the available reactive groups. If, however, after forming the amide at a temperature between l40-25 0 C., but usually not above 200 C., one heats such products at a higher range, ap proximately 250-280 C., or higher, possibly up to 300 C. for a. suitable period of time, for example, 1-2 hours or longer, one can in many cases recover a second mole of water for each mole of carboxylic acid employed, the first mole of water being evolved during amidification. The product formed in such cases is believed to contain a cyclic amidine ring such as an imidazoline or a tetrahydropyrimidine ring.

Ordinarily the methods employed for the production of amino imidazolines result in the formation of substantial amounts of other products such as amido imidazolines. However, certain procedures are well known by which the yield of amino imidazolines is comparatively high as, for example, by the use of a polyamine in which one of the terminal hydrogen atoms has been replaced by a low molal alkyl group or an hydroxyalkyl group, and by the use of salts in which the polyamine has been converted into a monosalt such as combination with hydrochloric acid or paratoluene sulfonic acid. Other procedures involve reaction with a hydroxyalkyl ethylene diamine and further treatment of such imidazoline having a hydroxyalkyl substituent with two or more moles of ethylene imine. Other well known procedures may be employed to give comparatively high yields.

Other very useful derivatives comprise acid salts and quaternary salts,derived therefrom. Since the compositions contain basic nitrogen groups, they are capable of reacting with inorganic acids, for example hydrohalogens (HCl, HBr, HI), sulfuric acid, phosphoric acid, etc., aliphatic acids (acetic, propionic, tglycolic, diglycolic, etc), aromatic acids (benzoic, salicylic, phthalic, etc.) and organic compounds capable of forming salts, for example, those having the general formula RX wherein R is an organic group, such 'as an valkyl group .(eg. methyl, ethyl, propyl, butyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, oleyl, octadecyl, etc.), cycloalkyl (erg. cyclo pentyl, cyclohexyl, etc.), aralkyl (eg. benzyl, etc.), and the like, and X is a radical capable of forming a salt such. as those derived from acids (e.g. halide, sulfate, phosphate, sulfonate, etc., radicals). The preparation of these salts and quaternary compounds is well known to the chemical art. For example, they may be prepared by adding suitable acids (for example, any of those mentioned herein as acylating agents) to solutions of the basic composition or by heating such compounds as alkyl halides with these compositions. Diacid and quaternary salts can also be formed by reacting alkylene dihalides, polyacids, etc. The number of moles of acid and quaternary compounds that may react with the composition of this invention will, of course, depend on the number of basic nitrogen groups in the molecule. These salts may be represented by the general formula N+X-, wherein N comprises the part of the compound containing the nitrogen group which has been rendered positively charged by the H or R of the alkylating compound and X represents the anion derived from the alkylating compound.

THE METHYLOL PHENOL As previously stated, the methylol phenols include monophenols and diphenols. The methylol groups on the phenol are either in one or two ortho positions or in the para position of the phenolic rings. The remaining phenolic ring positions are either unsubstituted or substituted With groups not interfering with the amine methylol condensation. Thus, the monophenols have 1, 2 or 3 methylol groups and the diphenols contain 1, 2, 3 or 4 methylol groups.

The following is the monophenol most advantageously employed:

l OHzOH This compound, 2,4,6 trimethylol phenol (TMP) is available. commercially in 70% aqueous solutions. The designation TMP is sometimes used to designate trimethylol propane. Apparently no confusion is involved, in light of the obvious differences.

A second monophenol which can be advantageously employed is:

where R is an aliphatic saturated or unsaturated hydrocarbon having, for example, 130 carbon atoms, for example, methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, amyl, tort-amyl, hexyl, tert-hexyl, octyl, nonyl, decyl, dodecyl, octo-decyl, etc., the corresponding unsaturated groups, etc.

The third monophenol advantageously employed is:

HO OH CHQOH l CH2OH Where R comp-rises an aliphatic saturated or unsaturated hydrocarbon as stated above in the second monophenol, for example, that derived from cardanol or hydrocardanol.

The following are diphenol species advantageously employed:

One species is 0112011 OHZOH Where R is hydrogen or a lower alkyl, preferably methyl.

A second species is OH on I f" E0 0H2- --0 43112011 Where R has the same meaning as that of the second species of the monophenols and R is hydrogen or a lower alkyl, preferably methyl.

We can employ a wide variety of methylol phenols in the reaction, and the reaction appears to be generally applicable to the classes of phenols heretofore specified. Examples of suitable methylol phenols include:

Monophenols:

Z-methylol phenol 2,6-dimethylol, 4- methy1 phenol 2,4,:6-trimethylol phenol 2,6-dirnethylol, 4-cyclohexyl phenol 2,6-dimethylol-4-phenyl phenol 2,6-dimethylol-4-methoxyphenol 2,6-dimethylol-4-chlorophenol 2,6-dimethy-lol-3 -methylphenol 2,6-dimethylol-4-sec-butylpheno1 2,6-dimethy1ol,3,5 -dimethyl-4-chlorophenol 2,4,6-trimethylol, 3-pentadecyl phenol 2,4,6-trimethylol, 3-pentadecadienyl phenol Diphenols onion omen l 011,011 0112011 (IJHaOH onion 011,011 OHzOH E r e CHzOH HZOH CHzOH on on, nron Q O 01120131 OHzOH on on HOCH2-OOH2OCH2OH onion CHzOH on CH3 I v HOCHzl- CHzOH in,

on OH I (IT/Ha I HO-OHr (IJ 011,011 on,

on, on,

CHzOH CHzOH r no o on G a GHZOH onion omon onion onion (JHZOH CHZOH onion 1 o t HO OH I CHzOH CHzOH H n1 HOCHPOS1QOCHZOH I C1732: rzHzr onion onion T I f I CHzOH CHaOH 011,011 CHzOH I h) a I o CHZOH omoH onion omen CHZOH onion Examples of additional methylol phenols which can be employed to' give the useful products of this invention are described in The Chemistry of Phenolic Resins, by Robert W. Martin, Tables V and VI, pp. 32-39 (Wiley,

THE POLYAMINE As noted previously, the general formula for the polyamine is groups. Thus, the term polyamine includes compounds having one amino group on one kind of radical, for example, an aliphatic radical, and another amino group on the heterocyclic radical as in the case of the following formula:

provided, of course, the polyamine has at least one secondary amino group capable of condensing with the methylol group. It also includes compounds which are totally heterocyclic, having a similarly reactive secondary amino group. It also includes polyamines having other elements besides carbon, hydrogen and nitrogen, for example, those also containing oxygen, sulfur, etc. As previ-ously stated, the preferred embodiments of the present invention are the alkylene polyamines, the hydroxylated alkylene polyamines and the amino cyclic Polyamines are available commercially and can be prepared by well-known methods. It is well known that olefin dichlorides, particularly those containing from 2 to 10 carbon atoms, can be reacted with ammonia or amines :to give alkylene polyamiues. If, instead of using ethylene dichloride, the corresponding propylene, butylene, amylene or higher molecular weight dichlorides are used, one then obtains the comparable homologues. One can also use alpha-omega dialkyl ethers such as and the like. Shrch polyamines can be alkylated in the manner commonly employed for alkylating monoamines. Such alkylation results in products which are symmetrically or non-symmetrically alkylated. The symmetrically alkylated polyamines are most readily obtainable. For instance, alkylated products can be derived by reaction between alkyl chlorides, such as propyl chloride, butyl chloride, amyl chloride, cetyl chloride, and the like and a polyamine having one or more primary amino groups. Such reactions result in the formation of hydrochloric acid, and hence the resultant product is an amine hydrochloride. The conventional method for conversion into the base is to treat with dilute caustic solution. Alkylation is not limited to the introduction of an alkyl group, but as a matter of fact, the radical introduced can be characterized by a carbon atom chain interrupted at least once by an oxygen atom. In other Words, alkylation is accomplished by compounds which are essentially alkyloxyalkyl chlorides, as, for example, the following:

The reaction involving the alkylene dichlorides is not limited to ammonia, but also involves amines, such as ethylamine, propylamine, butylamine, octylamine, decylamine, cetylamine, dodecylamine, etc. Cycloaliphatic and aromatic amines are also reactive. Similarly, the reaction also involves the comparable secondary amines, in which various alkyl radicals previously mentioned ap pear twice and are types in which two dissimilar radicals appear, for instance, amyl butylamine, hexyl octylamine, etc. Furthermore, compounds derived by reactions involving alkylene dichlorides and a mixture of ammonia and amines, or a mixture of two different amines are useful. However, one need not employ a polyamine having an alkyl radical. For instance, any suitable polyalkylene polyamine, such as an ethylene polyamine, a propylene polyamine, etc., treated with ethylene oxide or similar oxyalkylating agent are useful. Furthermore, various hydroxylated amines, such as monoethanolamine, monopropanolamine, and the like, are also treated with a suit- 9 able alkylene dichloride, such as ethylene dichloride, propylene dichloride, etc.

As to the introduction of a hydroxylated group, one can use any one of a number of well-known procedures such as alkylation, involving a chlorhydrin, such as ethylenechlorhydrin, glycerol chlorhydrin, or the like. Such reactions are entirely comparable to the alkylation reaction involving alkyl chlorides previously described. Other reactions involve the use of an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, styrene oxide or the like. Glycide is advantageously employed. The type of reaction just referred to is well known and results in the introduction of a hydroxylated or polyhydroxylated radical in an amino hydrogen position. It is also possible to introduce a hydroxylated oxyhydrocarbon atom; for instance, instead of using the chlorhydrin corresponding to ethylene glycol, one employs the chlorhydrin corresponding to diethylene glycol. Similarly, instead of using the chlorhydrin corresponding to glycerol, one employs the chlorhydrin corresponding to diglycerol.

From the above description it can be seen that many of the above polyamines can be characterized by the general formula where the Rs, which are the same or different, comprise hydrogen, alkyl, cycloalkyl, aryl, alkyloxyalkyl, hydroxylated alkyl, hydroxylated alkyloxyalkyl, etc., radicals, x is zero or a whole number of at least one, for example 1 to 10, but preferably 1 to 3, provided the polyamine contains at least one secondary amino group, and n is a whole number, 2 or greater, for example 2-10, but preferably 2-5. Of course, it should be realized that the amino or hydroxyl group may be modified by acylation to form amides, esters or mixtures thereof, prior to the methylol-amino condensation provided at least one active secondary amine group remains on the molecule. Any of the suitable acylating agents herein described may be employed in this acylation. Prior acylation of the amine can advantageously be used instead of acylation subsequent to amine condensation.

A particularly useful class of polyamines is a class of branched polyamines. These branched polyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylene group per nine amino units present on the main chain, for example 1-4 of such branched chains per nine units on the main chain, but preferably one side chain unit per nine main chain units. Thus, these polyamines contain at least three primary amino groups and at least one tertiary amino group in addition to at least one secondary amino group.

These branched polyamines may formula be expressed by the 24 or more but preferably 6 to 18, y being for example 1 to 6 or more but preferably 1 to 3, and 2 being for exit ample 0-6 but preferably 0-1. The x and y units may be sequential, alternative, orderly or randomly distributed. The preferred class of branched polyamines includes those of the formula where n is an integer. for example 1-20 or more but preferably 1-3, wherein R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched).

The particularly preferred branched polyamines are presented by the following formula:

The radicals in the brackets may be joined in a headto-head or a headto-tail fashion. Compounds described by this formula wherein n=l-3 are manufactured and sold by Dow Chemical Company as Polyamines N-400, N-SOO, N-l200, etc. Polyamine N-400 has the above formula wherein n=1 and was the branched polyamine employed in all of the specific examples.

The branched polyamines can be prepared by a wide variety of methods. One method comprises the reaction of ethanolamine and ammonia under pressure over a fixed bed of a metal hydrogenation catalyst. By controlling the conditions of this reaction one can obtain various amounts of piperazine and polyamines as well as the branched chain polyalkylene polyamine. This process is described in Australian Patent No. 42,189 and in the East German Patent 14,480 (March 17, 1958) reported in Chem. Abstracts, August 10, 1958, 14129.

The branched polyamines can also be prepared by the following reactions:

(:JHE I t.

Triethylene tetramine Variations on the above procedure can produce other branched polyamines.

The branched nature of the polyamine imparts unusual properties to the polyamine and its derivatives. Cyclic f N(C nH2n O C nH2nN)C nHZnOOnHZnN or mixtures of these groups and alkylene groups, for example,

/R DHZnN N CnHZnO OnHZuN/ O R X where R, n and x has the meaning previously stated for the linear polyamine.

For convenience the aliphatic polyamines have been classified as nonhydroxylated :and hydroxylated alkylene polyamino amines. The following are representative members of the nonhydroxylated series:

Diethylene triamine, Dipropylene tr-iamine, Dibutylene triamine, etc. Triethylene tetramine, Tripropylene tetramine, Tributylene tetramine, etc., Tetraethyleue pentamine, Tetrapropylene pentamine, Tet-arbutylene pentamine, etc., Mixtures of the above, Mixed ethylene, propylene, and/or butylene, etc., polyamines and other members of the series.

The above polyamines modified with higher molecular weight aliphatic groups, for example, those having from 8-30 or more carbon atoms, a typical example of which is NH2 C2H4N- C2H4N C 2H4N- C is aa where the aliphatic group is derived from any suitable source, for example, from compounds of animal or vegetable origin, such as coconut oil, tallow, tall oil, soya, etc., are very useful. In addition, the polyamine can contain other :alkylene groups, fewer amino groups, additional higher aliphatic groups, etc., provided the polyamine has at least one reactive secondary amino group. Compositions of this type are described in US. Patent 2,267,205.

Other useful aliphatic polyamines are those containing substituted groups on the chain, for example, aromatic groups, heterocyclic groups, etc., such as a compound of the formula H NE -CH2OH-OHz-N-OHrfiJH-OHzNHa OH OH is reactive.

5 amino groups include the following:

'Polyamines containing aromatic groups in the main part of the chain are useful, fol-example, N,N-dimet-hylp-xylylenediamine.

Examples of polyamines containing solely secondary include the following:

I HNR wherein R is a hydrocarbon group,

GHQ-CH2 H1 1 (OH2NH) :H

where x: 1-5.

Z-undecylimidazoline 2-heptadecylimidazoline 2-oleylimidazoline l-N-decylaminoethyl, Z-ethylimidazoline Z-rnethyl, l-hexadecylaminoethylaminoethylimidazoline 1-dodecylaminopropylimidazoline l-( ste aroyloxyethyl) aminoethylamidazoline l-stearamidoethylaminoethylimidazoline Z-heptadecyl, 4-5-dimethylimi-dazoline l-dodecylaminohexylimidazoline l-stearoyloxyethylaminohexylirnidazoline Z-heptadecyl, l-methylaminoethyl tetrahydropyrimidine 4-methyl, Z-dodecyl, l-rnethylazninoethylaminoethyl tetrahydropyrimidine N C Hz C l'l 35 C N- C H:

C 2H4 O H C ZHgN As previously stated, there must be reacted at least one mole of polyamine per equivalent of methylol group. The upper limit to the amount of amine present will be determined by convenience and economics, for example, 1 or more moles of polyamine per equivalent of methylol group can be employed.

The following examples are illustrative of the preparation of the polyaminomethylol phenol condensate and are not intended for purposes of limitation.

The following general procedure is employed in preparing the polyamine-methylol condensate. The methylol-phenol is generally mixed or slowly added to the polyamine in ratios of 1 mole of polyamine per equivalent of methylol group on the phenol. However, where the polyamine is added to the methylolphenol, addition is carried out below 60 C. until at least one mole of polyamine per methylol group has been added. Enough of a suitable azeotroping agent is then added to remove water (benzene, toluene, or xylene) and heat applied. After removal of the calculated amount of water from the reaction mixture (one mole of water per equivalent of methylol group) heating is stopped and the azeotroping agent is evaporated ofi under vacuum. Although the reaction takes place at room temperature, higher temperatures are required to complete the reaction. Thus, the temperature during the reaction generally varies from 80l60 C. and the time from 4-24 hours. In general,

ia the reaction can be effected in the lower time range employing higher temperatures. However, the time test of completion of reaction is the amount of water removed.

Example 1a This example illustrates the reaction of a methylolmonophenol and a polyamine. A liter flask is employed with a conventional stirring device, thermometer phase separating trap condenser, heating mantle, etc. 70% aqueous 2,4,6 trimethylol phenol which can be prepared by conventional procedures or purchased in the open market, in this instance, the latter, is employed. The amount .used is one gram mole, i.e. 182 grams, of anhydrous trimethylol phenol in 82 grams of water. This represents three equivalents of methylol groups. This solution is added dropwise with stirring to three gram moles (309 grams) of diethylene triamine dissolved in ml. of xylene over about 30 minutes. An exothermic reaction takes place at this point but the temperature is maintained below approximately 60 C. The temperature is then raised so that distillation takes place with the removal of the predetermined amount of water, i.e., the water of solution as well as water of reaction. The water of reaction represents 3 gram moles or 54 grams.

The entire procedure including the initial addition of the trimethylol phenol until the end of the reaction is approximately 6 hours. At the end of the reaction period the xylene is removed, using a vacuum of approximately 80 mm. The resulting product is a viscous water-soluble liquid of a dark red color.

Example 28a This example illustrates the reaction of monophenol and a branched polyamine. A one liter flask is employed equipped with a conventional stirring device, thermometer, phase separating trap, condenser, heating mantle, etc. Polyamine N-400, 200* grams (0.50 mole), is placed in the flask and mixed with 150 grams of xylene. To this stirred mixture is added dropwise over a period of 15 minutes 44.0 grams (0.17 mole) of a 7 0% aqueous solution of 2,4,6-trimethylol phenol. There is no apparent temperature change. The reaction mixture is then heated to C., refluxed 45 minutes, and 24 milliliters of water is collected (the calculated amount of water is 22 milliliters). The product is a dark brown liquid (as a 68% xylene solution).

Example 2d This example illustrates the reaction of a methylol diphenol.

One mole of substantially water-free a methylol- OH2OH 0112013 3 I H3 I OHzOH OHzOH Example 5b In this example, 1 mole of substantially water-free HOCH2 CH2OH Oiz rs is reacted with 2. moles of -Duomeen S (Armour Co.),

: Example 28b This experiment is carried out in the same equipment as is employed in Example 28a except that a 300 milliliter flask is used. Into the flask is placed 50 grams of xylene .and 8.4 'grams (0.05 mole) of 2,6-dimethylol-4- methylphenol are added. The resulting slurry is stirred and warmed up to 80 C. Polyamine N-400, 40.0 grams (0.10 mole) is added slowly over a period of 45 minutes.

Solution takes place upon the addition of the polyamine. The reaction mixture is refluxed for about 4 hours at 140 C. and 1.8 milliliters of Water is collected, the calculated amount. The product, as a xylene solution, is a brown liquid.

Example 29b This experiment is carried out in the same equipment and in the same manner as is employed in Example 28b. To a slurry of 10.5 grams (0.05 mole) of 2,6-dimethylol- 4-tertiarybutylphenol in 50 gramsof xylene, 40 grams (0.10 mole) of Polyamine N-4OO are added all at once with stirring and the mixture is heated and refluxed at 140 C. for 4 hours with the collection of 1.6 milliliters of water. The calculated amount of water is 1.8 milliliters. The product, as a xylene solution, is reddish brown.

Example 30]) This experiment is carried out in the same equipment and in the same manner as is employed in Example 28b. To a slurry of 14.0 grams of 2,6-dimethylol-4-nonylphenol in 50 milliliters of benzene, 40.0 grams (0.10 mole) of Polyamine N-400 are added all at once with stirring and the mixture is heated and refluxed at 140 C. for 6 hours with the collection of 1.8 milliliters of water. The calculated amount of water is 1.8 milliliters. The product, as a xylene solution, is dark brown. V V V V The following amino-methylol condensates shown in Tables I-IV are prepared in the manner of Examples 1a, 2d, and 5b. In each case one mole ofpolyamine per equivalent of methylol group on the phenol is reacted and the reaction carried out until, taking into consideration the Water originally present, about one mole of water is removed for each equivalent of methylol group present on the phenol.

The pH ofrthe reaction mixture is determined solely by the reactants .(i.e., no inorganic base, such as Ca(OI-I) NaOI-I, etc. or other extraneous catalyst is present). Examples 1a, 2d, and 5b are also shown in the tables. Attempts are made in the examples to employ commercially available materials where possible. In the following tables the examples will be numbered by a method which will describe the nature of the product. The polyamine-methylol condensate will have a basic numben'for example, la, 4b, 6c, 4d, wherein those in the a series are derivedfrom TMP, the b series fi-om DMl, the c series from trimethylol cardanol and side chain hydrogenated cardanol (i.e., hydrocardanol), and the d series from the tetramethylol diphenols. The basic number always refers to the same amino condensate. The symbol A before the basic number indicates that the polyami-ne had been acylated prior to condensation. The symbol A after the basic number indicates that acylation takes place after condensation.

A2511 means that the 25a (amino condensate) was prepared from an amine which had been acylated prior to condensation. However, IOaA means that the condensate was acylated afiter condensation. The symbol 0 indicates oxyalkylation. Thus IOaAO indicates that the amine condensate 10a has been acy-l'ated (IOaA), followed by oxyalkylation. IOaAOA means that the same condensate, 10a, has been acylated (lOaA), then oxyalkylated (IOaAO) and then acylated. In other words, these symbols indicate both kind and order of treatment.

TABLE I Reaction of E0 CH CH;OH (designated TMP) and polyamines I CHzOH Molar ratio TMP to amine 1:3

Example Polyamine Diethylene traimine Triethylene tetramine Tetra-ethylene pentamine Dipropylene triamine Duomeen S (Armour 00.)

H R-NCH2C nCH2NH2 R derived from soya oil 6a Duomeen T (Armour Co.)

RI ICH CH CH;NHa

R derived from tallow Oxyethylated Duomeen S H C2H4OH RNCH2CH2CH2N 8a Oxyethylated Duomeen T H canon R N CHXCHZCH2N f H Amine ODT (Monsanto) N-methyl propylene diamrne N,N-dihydroxyethyl proplyleue diamine 18a N,N-dihydroxypropyl propylene diamine I V CHLOE 19a noo1H4 GzH40-c,H.oo.H,N

NCH;' y 20a CnHaaC N-CH H /N VCH2 21a CHiC Y N-om TABLE I-Continued Polyamine Example Polyamine N-CH:

240 C Hq C DIP-CH: H

10 A2511 Oleleacid prior acylated trlethylene tetremlne (1:1 molar ratlo) A260 Steal-i0 aeiq prior acylatecl tel r eethylene pen fiemine (1:1

molar ratl A270 Laurie ecid prior acylated tetraethylene pentamine (1:1

molar ratio) 280 I olyamine N400 The p 'oducts formed in the above Table I are dark, viscous liquids Reaction of HOCHa- TABLE II CH; QH (designated DMP) with polyamines Mole; rat io DMP/amine 1:2

Polyamine Dodecyl Octadecyh.

Oetadecyl Mixed secand tert-butyl- 8b-"-. Dodecyl 9b tert-Butyl Octadecyl tert-Butyl Diethylene triamine Triethylene ten-amine Tetraethylene pentamine Dipropylene triamine Duemeen S (Armour 00.)

H R-N-CHzC-HaCHaNH:

R derived from soya oil Duomeen T (Armour Co.)

H CuH:5N-C 2HNC 1H4NH:

Qxyethylated amine ODT v CaHgOH H C12 2:gCzHNC2HN N-(2-hydroxyethyl)-2-methy1-1,2 propanediamine N-methyl ethylene diamine N,N-dimethyl ethylene diamine Hydroxyethyl ethylene diamine N,N-dihydroxyethylethylene diamine N-methyl propylene diamine N,N-dihyd.roxyethy1 propylene diamine N,N-dihydroxypropy1 propylene dianzune TABLE IIContinued Polyamine Dodecyl n saG N- C H] N-CH: H t

viscous liquids.

The products formed in the above Table H are dark TABLE II-IContinued R derived from- Hydrogenated R derived from tallow TABLE III Ex. Rderived fro m- Polyamite OH CH,0H 7c--. Oardanol Oxyethylated Duomeen S ClHOH H R-N-CHZCHaCHaN R I H CHiOH 8c Hydrogenated Oxyethylated Duomeen T (trimethylol cardanol and side chain hydrogenated cardanol) with cardanolmammes 01114011 Molar ratio of the trimethylol cardanol to amine 1:3 H

R-N-CH1CH2CH2N\ Polyamine H 7 9c.. Cardanol Amine ODT (Monsanto) Diethylene triamine Triethylene tetraminem H Tetraethylene pentamine C1,H1;IICQH4N-CQH|NHQ Dipropylene triamine Duomeen S (Armour Co.) 100-. flydlggenlated Oxyethylated Amine ODT 7 car ano H CzHiOH R-N-CHgCH CH NH, V H

, C12H75-NC:H4NC1H4N R derived from soya oil 7 V H H Duomeen T (Armour Co.) 1111.. Cardanol N -(2-llydroxyethyl)-2-methyl-1,2-propanediamine H V 12c Hydrogenated N-methyl ethylene diamine RN CH1CH7CH1NH3 cardanol.

r; The products formed in the above Table III are dark, viscous liquids.

(Tetramethylol diphenol) with polyamine Molar ratio of tetramethylol diphenol to polyarmne 1:4

Ex. R Polyamine 1d--- Hydrogen Diethylene triamine 211... do Triethylene tetramine 3d Tetraethylene pentamine Dipropylene triamiue Duomeen S (Armour Co.)

R derived from soya oil N- (2-hydr0xyethyl)-2-methyl-1,2 propanediamins N-methyl ethylene diamine Diethylene Triamine Triethylene Tetramine Tetraethylene Pentamine Dipropylene Triamine Duomeen S (Armour Co.)

H R--N-CH3 C H2 C HQNH,

It derived from soya oil 2 2 TABLE IV-Continued Ex. R Polyarnlne 22d do Oxyethylated Amine ODT CzH4OH H H CuHg5-N-CzH N-CgH N 23d do N-(Z-hydroxyethyl)-2-methy1-l.Z-propanediamine 24d do N-methyl ethylene diamine The products formed in the above Table IV are dark, viscous liquids.

THE ACYLATING AGENT As in the reaction between the methylol phenol and the secondary amine, acylation is also carried out under dehydrating conditions, i.e., water is removed. Any of the well-known methods of acylation can be employed. For example, heat alone, heat and reduced pressure, heat in combination with an azeotroping agent, etc., are all satisfactory.

A wide variety of acylating agents can be employed. However, strong acylating agents such as acyl halides, or acid anhydrides should be avoided since they are capable of esterifying phenolic hydroxy groups, a feature which is undesirable.

Although [a wide variety of carboxylic acids produce excellent products, in our experience monocarboxy acids having more than 6 carbon atoms and less than 40 carbon atoms give most advantageous products. The most common examples include the detergent forming acids, i.e., those acids which combine with alkalies to produce soap or soap-1ike bodies. The detergent-forming acids, in turn, include naturally-occurring fatty acids, resin acids, such as abietic acid, naturally occurring petroleum acids, such as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As willbe subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat different sources and are different in structure, but can be included in the broad generic term previously indicated.

Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic, propionic, butyric, valen'c, caproic, heptanoic, caprylic, nonanoic, capric, nndecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, hep-tadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, doco san'oic, tricosanoic, tetracosanoic, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the ike.

Examples of ethylenic unsaturated aliphatic acids are acrylic, methacrylic, crotonic, angelic, tiglic, the pentenoic acids, the hexenoic acids, for example, hydrosorbic acid, the heptenoic acids, the octenoic acids, the nonenoic acids, the decenoic acids, for example, obtusilic acid, the un'decenoic acids, the dodecenoic acids, for ex ample, lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoic acids, for example, myristoleic acid, the pentadecenoic acids, the hexadecenoic acids, for example, palmitoleic acid, the heptadecenoic acids, the octodecenoic acids, for example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, 'for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetracosenoic acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadienoic acids, for example, sorbic acid, the octadien'oic acids, for example, linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, for example, linolenic acid, eleostearic acid, pseu acids, the hydroxypentadecanoic acids, the hydroxypal mitic acids, the hydroxyhexadecan'oic acids, the hydroxyheptadeca'noic acids, the hydroxy stearic acids, the hydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelardic acid, hydroxyo'ctadecenoic acids, for example, n'cinstearolic acid, the hydroxyeicosanoic acids, for example, hydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxybehem'c acid, and the like.

Exarriples of acetylated hydroxyacids are ricinoleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found in petroleum called naphthem'c acids, hydnocarpic and chaulmoognic acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, .campholic acid, fencholic acids, and the lik Examples ofaromatic monocarboxylic acids are benzoic acid, substituted benzoic acids, for example, the toluic acids,.:the xylenie acids, alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.

Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, coconut oil, rapeseed oil, sesame .oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydro genated animal and vegetable oils are advantageously employed. Fatty and similar acids include those derived fromvarious waxegsuch as beeswax, spermaceti, montan wax, japan wax, coce'erin and carnauba wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. One may also employ higher molecular weight carboxylic acids derived by oxidation and other methods, such as from paraflin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.

; Other suitable acids include phenylstearic acid, benzoylnonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, c'hlorstearic acid, etc.

Examples of the polycarboxylic acids are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suben'c, azelaic, sebacic, nonanedicarboxylic' acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are :Eu-maric, maleic, mesacenic, oitraconic, glutaconic, itaconic, muconic, aconitic acids, and the like.

Examples of aromatic polyearboxylic acids are phthalic, isophthalic acids, terephthalic acids, substituted denivati-ves thereof, (e.g. alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid, diphenylether dicariboxylic acids, diphenylsulfone dicarboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more than two carboxylic groups are hemimellitic, trimellitic, trimesic, mel-lophanic, prehnitic, pyromellitic acids, mellitic acid, and the like. i i

Other polycarboxylic acids are the dimeric, trimeric and polymeric acids, for example, dilinoleic, trilinoleic,

and other polyacids sold by Emery Industries, and the like. Other polycarboxylic acids include those containingether groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously employed.

In addition, acid precursors such as esters, glycerides, etc. can be employed in place of the free aci l The moles of acylating agent reacted with the polyaminomethy-l compound will depend on the number of acetylation reactive positions contained therein as -well as the number of moles one wishes to incorporate into the mole, cule. We have advantageously reacted 1 to 15 moles of acylating agent per mole of polya-minophenol, but preferably 3 to 6 moles.

The following examples are illustrative of the prepara-v tion of the acylated polyaminomethyl phenol condensate.

The following general procedure is employed in acylat-.

ing. The condensate is mixed with the desired ratio of acid and a suitable azeotroping agent is added. Heat is then applied. After the removal of the calculated amount of water l to 2 equivalents per mole of acid employed), heating is stopped and the azeotroping agent is evaporated under vacuum. The temperature during the reaction can vary from 80200 C. (except where the formation of the cyclic amidine type structure is desired and the maximum temperature is generally 2.00-2820 CI). The times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of water removed.

Example 3aA In a 5 liter, 3 necked flask furnished with a stirring device, thermometer, phase separating trap, condenser and heating mantle, 697 grams of 3a (one mole of the TMP- tetraethylene pentamine reaction product) is dissolved in 600 ml. of xylene. 846 grams of oleic acid (3 moles) is added to the TMP-polyamine condensate With stirring in ten minutes. The reaction mixture was then heated gradually to about in half an hour and then held at about over a period of 3 hours until 54 grams (3 moles) of water is collected in the side of'the tube. The solvent is then removed with gentle heating under a reduced pressure of approximately 20 mm. The product is a dark brown viscous liquid with a nitrogen content of 14.5%.

Example 30A The prior example is repeated except that the final reaction temperature is maintained at 240 C. and 90 grams (5 moles) of water is removed instead of 54 grams. Infrared analysis of the product indicates the presence of a cyclic amidine ring.

Example 7aA The reaction product of Example 7a (TMP and oxyethylated Duomeen S) is reacted with palmitic acid in the manner of Example 3aA. A xylene soluble product is formed.

The following examples of acylated polya-minomethyl phenol condensates are prepared in the manner of the above examples. The products obtained are dark viscous liquids.

Example 2812A Into a 300 milliliter flask, fitted with a stirring device, thermometer, phase separating trap, condenser and heating mantle, is placed a xylene solution of the product of Example 28a containing 98.0 grams (0.05 mole) of the reaction product of 2,4,6-trimethylolphenol and Polyamine N-400 and about 24 grams of xylene. To this solution is added with stirring 30.0 grams (0.15 mole) of lauric acid. The reaction mixture is heated for about one hour at a maximum reaction temperture of C. and 6 milliliters of Water are collected. The calculated amount of 25 water for imidazoline formation is 5.4 milliliters. The resulting product as an 88 percent xylene solution is a dark brown thick liquid.

Example 2812A Into a 300 milliliter flask, fitted with a stirring device, thermometer, phase separating trap, condenser and heating mantle is placed a xylene solution of the product of Example 28b containing 35.0 grams (0.025 mole) of the reaction product of 2,6-dimethylolA-methylphenol and Polyamine N-400 and about grams of xylene. To this solution is added with stirring 14.1 grams (0.05 mole) of oleic acid. The reaction mixture is heated at reflux for 4.5 hours at a maximum temperature of 183 C. and 1.0 milliliter of water is collected, the calculated amount of Water for amide format-ion being 0.9 milliliter. The product is a dark burgundy liquid (as 70.5% xylene solution).

Example 2911A This experiment is performed in the same equipment and in the same manner as employed in Example 28bA. Into the flask is placed a xylene solution of the product of Example 291; containing 40.9 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-tertiarybl1iyl phenol and Polyamine N-400 and about 47 grams of xylene. To this solution is added with stirring 7.2 grams (0.05 mole) of octanoic acid. The reaction mixture is heated at reflux for 3.75 hours at a maximum temperature of 154 C. and 1.3 milliliters of water is collected. The calculated amount of water for amide formation is 0.9 milliliter. The product as a 49.82 percent xylene solution was brown.

Example 3017A This experiment is performed in the same manner and in the same equipment as is employed in Example 28bA. Into the flask is placed a xylene solution of the product of Example 3017 containing 39.6 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-nonylpheno1 and TABLE VI.Acylated Products 01 TABLE II Grams of Grams of Example Acid acid used per water regram-mole of moved condensate Stearic 568 36 O 564 36 800 72 120 36 456 36 512 36 1, 200 36 564 36 564 36 660 36 564 36 564 36 512 36 240 72 564 36 1,128 72 564 36 564 36 400 36 564 40 288 52 Stearic 569 40 See Table V for footnotes 1 and 2.

TABLE VII.Acylated Products of Table III See Table V for footnotes 1 and 2.

TABLE VIII.-AOYLATED PRODUCTS OF TABLE IV Polyamine N-40O and about 32 grams of xylene. To Grails of G of this solution is added With stirring 14.2 grams (0.05 111016) Example Acid acid used per water reof stearic acid. The reaction mixture is heated at reflux moved for 4 hours at a maximum temperature of 160 C. and 1.0 milliliter of water is collected. The calculated amount 1 128 72 of water for amide formation is 0.9 milliliter. The prod- 1,128 72 uct as a 62.5% xylene solution is a brown liquid. 912 72 1,024 72 1,123 72 TABLE VrAcyIated Products of TABLE I 2 400 72 1,320 72 Grams of Grams of 1 Example Acid acidusedper waterre- {12g 72 gram-mole of moved 1' 128 72 condensate 1: 128 72 2, 0 1s 1% Ole 846 54 Nonanoic 31s 36 )22 846 54 11136 72 do- 846 90 1 13 72 Stearics52 54 1 12s 72 Laurie- 600 54 1 12s 72 Myristlc 684 54 1 12s 72 Palmitic--- 75s 54 1 12s 72 Propanoio 222 54 lglimeric 1,800 54 eic 846 54 nu-do-T n 846 54 See Table V for footnotes 1 and 2. p acid 990 54 Reference has been made and reference will be con- Olerc 846 54 1,536 103 turned to be made herein to oxyalkylation procedures. 1 23g 3% Such procedures are concerned with the use of mono- 1: 92 108 epoxides and principally those available commercially g? g: at low cost, such as ethylene oxide, propylene oxide and 600 120 butylene oxide, octylene oxide, styrene oxide, etc.

1 Dilinoleic acid sold by Emery Industries. Also employed in Examples of Tables VI, VII and VIII. 2 Naphthenic acid sold by Sun Oil Company, average molecular weight 220-230.

particular attention is directed to the various patents 2.7 which describe typical oxyalkylation procedure. Furthermore, manufacturers of alkylene oxides furnish exten sive information as to the use of oxides. For example, see the technical bulletin entitled Ethylene Oxide which has been distributed by the Iefierson Chemical Company, Houston, Texas. Note also the extensive bibliography in this bulletin and the large, number of patents which deal with oxyalkylation processes. A

The following examples illustrate oxyalkylationf] Example laA O The reaction vessel employed is a 4 liter stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means, etc., which are conventional. in, this type of apparatus. The stirrer is operated at a speed of 250 rpm. Into the autoclave is charged 1230fgrams,(1 mole) of laA, and 500 grams of xylene. The autoclave is sealed, swept with nitrogen, stirring started immediately, and heat applied. The temperature is allowed to rise to approximately 100 C. at which time the addition of ethylene oxide is started.

Ethylene oxide is added continuously at such speed that it is absorbed by the reaction mixture as added. During the addition 132 grams (3 moles) of ethylene oxide is added over 2% hours at a temperature of 100 C. to 120 C. and a maximum pressure of 30 psi Example JaAO The reaction mass of Example 1A0 is transferred to a larger autoclave (capacity 15 liters) similarly equipped. Without adding any more xylene the procedure is repeated so as to add another 264 grams (6 moles) of ethylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition. 7

Example 111,40

In a third step, another 264 grams (6 moles) of ethylene oxide is added to the product of Example IaAO The reaction slows up and requires approximately 6 hours, using the same operating temperatures and pressures.

Example 1 HA 0.;

g. (1 mole) of MA and 500 grams of xylene. The autoclave is sealed, swept with nitrogen, stirring is'started im- 'mediately, and heat is applied. The temperature is allowed to rise to approximatelyj100 C. at which time the addition of propylene oxide is started. Propylene oxide is added continuously at such speed that it is ab sorbed by the reaction mixture as added. During the addition 174 g. (3 moles) of propylene oxide are added over 2% hours at a temperature of 100 to 120 C. and a maximum pressure of 30 lbs. p.s.i. I]

Example laAO The reaction mass of Example 1aAO is transferred to a larger autoclave (capacity 15 liters). The procedure is repeated so as to add another 174 g. (3 moles) of propylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition.

Example 1aA0 At the end of the second step (Example MAO the autoclave is opened, 25 g. of sodium methylate is added, and the autoclave is flushed out as before. Oxyalkylation- 'is continued as before until another 522 g. (9 moles) of propylene oxide are added. 8 hours are required to complete the reaction. h

The following examples of oxyalkylation are carried out in the manner of the examples described above. A catalyst is used in the case of oxyethylation after the initial 15 moles of ethylene oxide are added, while in the case of oxypropylation, the catalyst is used after the initial 6 moles of oxide are added. In the case of oxybutylation, oxyoctylation, oxystyrenation, etc. the catalyst is added at the beginning of the operation. In all cases the amount of catalyst is about 1% percent of the total reactant'present. The oxides are added inthe order given reading from left toright. The results are presented in the following'tables:

Grams of Oxide Added per Gram Mole oi Condensate Example EtO PrO B TABLE X.--THE OXYALKYLATED PRODUCTS OF TABLE II Grams of Oxide Added per Gram Mole of Condensate Example EtO PrO BuO Octyleue Styrene oxide oxide TABLE XI.-THE OXYALKYLATED PRoDUo'rsoF TABLE. III 1 Grams of Oxide Added per 'Gram Mole of Condensate Octylene oxide Example EtO PrO BuO Styrene oxide TABLE XII.THE OXYALKYLATED PRODUCTS OF TABLE IV Grams of Oxide Added per Gram Mole of Condensate Example EtO PrO BuO Octylene oxide Styrene oxide TABLE XHL-THE OXYALKYLATED PRODUCTS OF TABLE V Grams of Oxide Added per Gram Mole oi Condensate Example EtO PrO BuO Octylene oxide TABLE XIV.THE OXYALKYLATED PRODUCTS OF TABLE VI Grams of Oxide Added per Gram Mole oi Acylated Product Example EtO PrO BuO Octylene Styrene oxide oxide TABLE XV.-THE OXYALKYLATED PRODUCTS OF TABLE VI Grams of Oxide Added per Gram Mole of Aoylated Product Example EtO PrO BuO Octylene oxide Styrene oxide TABLE XVL-THE OXYALKYLATED PRODUCTS 0F TABLE VII Grams of Oxide Added per Gram Mole of Acylatcd Product Example EtO PrO BuO Octylene Styrene oxide oxide Since the oxyalkylated, and the acylated and oxyalkylated products have terminal hydroxy groups, they can be acylated. This step is carried out in the manner previously described for acylation. These examples are illustrative and not limitin Example 1110A One mole (919 grams) of 1:10 mixed with 846 grams (three moles) of oleic acid and 300 m1. xylene. The reaction mixture is heated to about ISO-460 C. over a period of 2 hours until 54 grams (3 moies) of water are removed. Xylene is then removed under vacuum. The product laOA is xylene soluble.

Example laAOA The process of the immediately previous example is repeated using laAO. The product laAOA is xylene soluble.

Additional examples are presented in the following tables. All of the products are dark, viscous liquids.

TABLE XVII.THE ACYLATED PRODUCTS OF TABLES IX, X, XI, XII

Grams of acid per gram-mole of oxyalkylated product Grams water removed Example Acid WNDDOIIHHHHHHHHHHHHH camcammoomeoouoomoooeoooooooo Grams of acid 7 p per gram Grams Example Acid mole of w ater oxyalkylated removed product ASPHALT ADDITIVES This phase of the invention relates to the use of the aforementioned compounds in securing a satisfactory bond between bituminous compositions and the various surfaces to which they are applied in industrial operations, such as road-building. This problem is well-recognized, and many attempts have been made to overcome it. For example, see US. Patents Nos. 2,317,959, dated April 27, 1943, to Johnson et al.; 2,361,488, dated October 31, 1944, to Mikeska; 2,386,867, dated October 16, 1945, to Johnson; 2,508,428-9, dated May 23, 1950, to Smith et al.

In road-construction use, bituminous compositions are employed in conjunction with vaaious mineral materials, sometimes mineral materials like cinders or slags, but more usually of natural origin, such as sand, rock, etc. It is obvious that the potentially usable aggregates include all the various kinds of rock native to the localities where roads are to be built. For example, limestone, dolomite, silica, rhyolite, caliche, and sedimentary, metamonphic, or igneous rocks of various other kinds, are regularly used in road-building. Such mineral aggregates are hydrophilic in character, a fact that is generally considered to be principally responsible for the existence of the bitumenastripping problem.

When a bituminous substance such as asphalt, in molten, cutback, or emulsified form, is applied to such hydrophilic surfaces as those of mineral aggregates, (in road-building), concrete walls (in water-proofing), paper (in Water-proofing), etc, it is difiicult to secure prompt coating of the surfaces by the bituminous material. Further, it is diflicult to prevent the stripping or removal of such bituminous coating from such surfaces, with time. Prevention of stripping is the more important consideration, although ease of application is frequently of material importance.

Where the surface is moist, damp, or actually soaked, the problem is obviously intensified, because the bitumen .must not only coat the surface, but it must first dislodge a tenaciously held water film. Some aggregates are river gravels; when freshly dr edgeld th'ey come to the job saturated with water. Rainstorms occurring during construction also produce soaked aggregates and promote stripping. Some aggregates, like caliche, and some limestones and dolomites are quite porous and retain considerable water in the interstices afterthe outer surfaces of the particles seem reasonably. dry.

In some cases it has beennecessary first to 'dry the surface before applying the bituminous coating. Road- Ways laid in wet weather deteriorate rapidly'in use. Where a bituminous roadway is subjected to water, as in low-lying areas or areas Where Water run-01f is frequent or constant, it soon disintegrates, with the development 'of holes, The aggregate used in its construction is 32 easily broken down to individual pebbles or small clumps of pebbles under such conditions, in absence of some corrective or preventive procedure, such as drying the aggregate by heat, before use.

The bitumen additives or reagents of our invention,

when added in small proportions materially improve the bond between bituminous compositions and the surfacesto which they are applied. Stated another Way, they will effectively reduce the degree of stripping of such bituminous compositions from.- such surfaces. Reagents employed for such purpose are commonly termed antistrippers or asphalt anti-strippers.

.These compounds in very small proportions in such bituminous compositions are useful in road construction, in Water-proofing, and in coating surfaces of various kinds. Bituminous'compositions which include our reagents resist stripping from the surfaces to whichthey are applied. In other words, they are strip-resistant, as compared with the same bitumen used in absence of our reagents.

' Where the bituminous composition is to be 'used for water-proofing walls or paper or other surfaces, the mix ture of it with our reagents is the finished or complete composition.

Within the terms bitumen, bituminous composition's, bituminous materials, and similar expressions including the word bituminous, we mean to include natural asphalt, petroleum still residues of paving grade; plastic residues from coal tar distillation, petroleum pitch, solutions of such substances like cut-back asphalts, emulsions thereof, and the like.

To accomplish the foregoing objectives, the agents of our invention are'required to be employed in only very small proportions, generallynot more than 1% by Weight of such reagents based on the weight of the bituminous component, butpreferably 0.1% to 0.8%, being suflicient satisfactorily to control stripping. However, larger amounts may be employed if desired. While our reagents are highly effective when used in absence of other available additives, they are useful in conjunction with, or admixed with, any other effective and compatible anti-stripper. For example, US. Patent No. 2,392,863, dated January 15, 1946, to Rudd, claims tall oil as an anti-stripper. Our reagents are generally compatible with tall oil, and are used for their present purpose in the presence of tall oil, or can be applied in the form of an admixture with tall oil.

Ordinarily, our reagents are added to or incorporated in the bituminous component before it is incorporated into any mixture. For example, they are added to molten If desired, our reagents are added to the mixer in which the bituminous material and the mineral aggregate are being mixed.- In the case of bituminous emulsions, our reagents are added to the 55 femulsion after it has been produced or to the bituminous 'procedureof incorporating our reagents is not critical; the important thing is that they be as uniformly distributed throughout the finished composition as is possible.

component of such emulsions, before emulsification. The

For various reasons, including viscosity, we prefer to employ our reagents in the form of a solution in a suitable solvent. In some instances, especially where salt forms of our reagents are desired or required, water is the solvent selected, because of cost considerations. Where the reagent is water-insoluble or where water is unacceptable as a solvent, for temperature or other reasons, various organic solvents are employed. Aromatic petroleum solvent, sulfur dioxide extract, and petroleum 'distillates of various kinds, are useful. The solvent is not a material part of our invention Any suitable solvent .may be employed; usually the selection will be on, the 1 basis of cost. We prefer aromatic petroleum solvent be- 7 cause of its good solvent power and low cost. When our j preferred reagents, described above, are 'mixed with aromatic petroleum solvent in equal volumes, a solution of satisfactory viscosity is produced. It is the preferred form of employing reagents. Our reagents are often added to asphalt, for example, at the refinery. This is a desirable procedure where large volumes are to be handled or where the asphalt is so heavy-bodied as to require heating to insure uniform distribution of the antistripper. Where conditions in the field are such that adequate mixing is achieved, our reagents are often added there, as the asphalt is used. Reagents appear to be quite stable at the usual storage and working temperatures of asphalt.

If the reagent is added at the refinery, the following example of procedure is practicable; Place the bituminous material or asphalt in a tank containing heating coils and bring it to a temperature at which its viscosity is relatively low. Add 1 pound of either of our reagents (in the form of a 50 weight percent solution in aromatic petroleum solvent) to every 133 pounds of bitumen, a ratio of 0.75%. If the asphalt is SC-6 or penetration grade asphalt, considerable heating will be required to bring the asphalt to acceptable fiuide state. 'Pour in the desired proportion of reagent and mix it in the asphalt by rolling with gas, recycling through a mixing tank with mixing-type pumps, or stirring With a propeller or other tank-type stirrer. 'Ihe bituminous mixture so prepared is delivered to the job ready for use in any desired method of application.

There may be, for example, direct application by spraying it on already-laid aggregate; application to a continuous road-mixing unit; or addition to a hot-mix plant. The reagent-asphalt mixture may be sprayed or poured for seal-coat application in the conventional manner. The presence of the reagent does not adversely afiect the properties of the asphalt, or the application of the latter; the bituminous material is handled exactly as if no reagent had been added.

Where small batches of several-barrel size are involved, addition of the reagent may take place in the field, followed by hand stirring until a uniform distribution of reagent has been achieved.

Where the reagent is to be incorporated in an emulsified bituminous composition, it may be added to the bitumen ingredient in the manner just described; or it may be added to the finished emulsion by simply stirring it in the desired proportion in any conventional manner. The salt form of the reagent may be preferable in such latter instances. We have added our compounds in 50 weight percent solution in aromatic petroleum solvent to emulsified asphalt to produce a highly strip-resistant composition.

If desired, our reagents are added to and mixed with the aggregate before it is coated with the bituminous composition. While this is a less common procedure, it is perfectly feasible, especially where the reagent is sufficiently water-dispersible to give a reasonably stable dispersion which can be quite uniformly distributed throughout the aggregate.

A number of laboratory techniques have been proposed to evaluate anti-strippers. All or nearly all of them include the operation of coating some surface with a bituminous composition, subjecting the coated surface to stripping conditions, and appraising the degree :of stripping that has taken place. Our reagents demonstrate their efiectiveness strikingly in such tests.

One such test (Test 1) subjects a measured amount of mineral aggregate to a measured amount of water; thereafter coats the aggregate with the bitumen or bitumenadditive mixture; cures or ages the coated sample for a definite period of time; then strips the coated aggregate with water at a definite temperature and for a definite time; and thereafter, usually by visual examination, determines the percentage of the aggregate particles that have been stripped of their original bituminous coating.

The following examples are presented to illustrate this phase of the present invention:

The anti-stripping agents are tested according to the general procedure of Test #1, described above, by mixing 0.5% by weight of the anti-stripping agents listed in the table below into a MC-3 asphalt heated to about 200- 275 F. This asphalt mixture is then used to coat a wet rock aggregate containing about 2% by weight of water (San Gabriel #4 crushed). The coated aggregate (as well as a control containing no anti-stripping agent) is then aged for 20 hours at room temperature. At the end of this time water (3 times the weight of the coated aggregate) is added and this mixture is stirred for 5 minutes at 150-175 Thereupon the coated aggregates are examined to determine the percentage of the aggregates that have been stripped of their asphalt coating. In all cases aggregates containing the composition shown in the following table are superior to the control.

Anti-stripping agent I Ex. No. Weight of H20 oxides added Reactants (grams) elimito I (grams) nated 11-l 1a (439) plus oleic acid (846) 54 None. 11- lo 54 EtO (132) 11-3" do 54 E (264) 11-4 2a (568) plus stearic acid (852) 54 e. 11-5" o 72 EtO (132) 11-6-- 3a (679) plus oleic acid (846) 54 1 e. 117 .(10 72 EtO (132) 11-8.- 4a (523) plus oleic acid (845) 54 Do. 11-9 1a (439) plus nonanoic acid (475).. 54 e. 1110 do 54 EtO (132) 1111 117 (492) plus lauric acid (400) 36 e. 1l12 o 36 EtO (88) 11-13 10 (645) plus lauric acid (60 54 us. 11-14 0 54 EtO (132) 11-15 1d (660) plus oleic acid (1,128) 72 e. 11l6 o 72 13130 (176) 11-17 3d (1,004) plus lauric acid (800) 72 J. ne. 11-18 o '12 E110 (176) 11-19 1611 (800) plus lauric acid (800)- 72 None. 1120 do 72 EtO (176) 11-21 10a (1,075) plus lauric acid (600) 54 None. 1122 7a (1,462) plus lauric acid (600)--- 54 Do.

Anti-stripping agent I II Ex. No. H O Weight of oxides Reactants (grams) elimiadded to I in alphanated betical order (grams) 11-23 28a (1,960) (A) PrO (580). 11-24. 2811 (1,960) plus lauric acid 120 (A) PrO (116), (B)

600 EtO (1,320). 11-25 28110 (3.054) plus stcaric acid 18 (284). 11-26. 1127 2812 (1,400) E (1,980). 11-28 28b (1,400) plus oleic acid (564). 40 EtO (2,640). 1129 28bAOA 11-30. 29b (1,635) (A) Pro (522), (B)

EtO (1,980). 11-31. 29b (1,635) plus oleic acid (282)- 18 EtO (1,320). 1132 29I()2%2)(2,655) plus oleic acid 18 11-33. 29bAOA 11-34 30b (1,580) EtO (2,200). 11-35 mtg 15580) plus stearic acid 40 O0 1136 do 40 (A) PrO (464), (B)

11-37. 30bAOA We claim:

1. A strip-resistant bituminous composition containing an asphalt and a minor amount of a member selected from the group consisting of:

(1) acylated, (2) oxyalkylated, (3) acylated then oxyalkylated, (4) oxyalkylated then acylated, (5) acylated, then oxyalkylated and then acylated, monomeric polyaminomethyl phenols characterized by reacting a containing at least one secondary amine group in amounts of at least one mole of secondary polyamine per equivalent of methylol group on the phenol until one mole of water per equivalent of methylol group is removed, in the absence of an extraneous catalyst; and then reacting the thus formed monomeric polyaminomethyl phenol with a member selected from the group consisting of (1) an acylation agent, (2) an oxyallgylation agent, (3) an acylation then an oxyalkylation agent, (4) an oxyalkylation then an acylation agent, and (5) an acylation then on oxyalkylation and then an acylation agent, the preformed methylol phenol having only functional groups selected from the class consisting of methylol groups and phenolic hydroxyl groups, the polyamine having only functional groups selected from the class consisting of primary amino groups, secondary amino groups and hydroxyl groups, the acylation agent having up to 40 carbon atoms and being selected from the class consisting of unsubstituted carboxylic acids, unsub stituted hydroxy carboxylic acids, unsubstituted acylated hydroxy carboxylic acids, lower alkanol esters of unsubstituted carboxylic acids, glycerides of unsubstituted carboxylic acids, unsubstituted carboxylic acid chlorides and unsubstituted carboxylic acid anhydrides, and the oxyalkylation agent being selected from the class consisting of alpha-beta alkylene oxides and styrene oxide.

2. The composition of claim 1 where the preformed methylol phenol has all available ortho and para positions substituted with methylol groups.

3. The composition of claim 1 where the preformed methylol phenol is 2,4,6-trimethylol phenol;

4. The composition of claim 1 where the polyamine is an aliphatic polyamine.

5. The composition of claim 1 where the polyamine is a polyalkylene polyamine.

6. The composition of claim 1 where the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms.

7. The composition of claim 1 where the preformed methylol phenol is 2,4, 6-trirnethylol phenol, the polyamine is a polyalkylene polyamine, the acylationagent is a monocarboxy acid having 7 to 39 carbon atoms, and the oxyalkylation agent is at least one 1,2-alkylene oxide having 2 to 4 carbon atoms. 7 I

8. The composition of claim 1 where the member is an acylated monomeric polyarninomethyl phenol.

9. The composition of claim 1 where the member is an acylated then oxyalkylated monomeric polyaminomethyl phenol.

10. The compositions of claim 8 where the preformed methylol phenol is 2,4, 6-trimethylol phenol, the polyamine is a polyalkylene polyamine, and the acylation agent is a monocarboxy acid having 7 to 39 carbonatoms.

11. The composition of claim 9 where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is a polyalkylene polyamine, the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms, and the oxyalkylation agent is at least one 1,2-alkylene oxide.

12. The composition of claim 10 where the preformed methylol phenol is 2,4,-6-trimethylo1 phenol, the polyamine is diethylene triamine, and the acylation agent is oleic acid.

13. The composition of claim 10 where the preformed methylol phenol is 2,4, 6-trimethylol phenol, the polyamine is triethylene tetramine, and the acylation agent is stearic acid.

14. The composition of claim 10 methylol phenol is 2,4,6-trimethylol phenol, the polyamine is tetraethylene pentamine, and the acylation agent is oleic acid.

15. The composition of claim 11 where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is diethylene triamine, the acylation agent is oleic acid,

and the oxyalkylation agent is ethylene oxide.

16. The composition of claim 11 Where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is triethylene tetramine, the acylation agent is stearic acid, andthe oxyalkylation agent is ethylene oxide.

References Cited in the file of this patent UNITED STATES PATENTS 2,962,531 Coflield Nov. 29, 1960 where the preformed I 

1. A STRIP-RESISTANT BITUMINOUS COMPOSITION CONTAINING AN ASHPALT AND A MINOR AMOUNT OF AMOUNT OF A MEMBER SELECTED FORM THE GROUP CONSISTING OF: (1) ACYLATED, (2) OXYALKYLATED, (3) ACYLATED THEN OXYALKYLATED, (4) OXYALKYLATED AND THEN ACYLATED, (5) ACYLATED, THEN OXALKYLATED AND THEN ACYLATED, MONOMERIC POLYAMINOMETHYL PHENOLS CHARACTERIZED BY REACTING A PREFORMED METHYLOL PHENOL HAVING ONE TO FOUR METHYLOL GROUP IN THE 2, 4, 6, POSITION WITH A POLYMMINE CONTAINING AT LEAST ONE SECONDARY AMINE GROUP IN AMOUNTS OF AT LEAST ONE MOLE OF SECONDARY POLYMAINE PER QUIVALENT OF METHYLOL GROUP ON THE PHENOL UNTIL ONE MOLE OF WATER PER EQUIVALENT OF METHYLOL GROUP IS REMOVED, IN THE ABSENCE OF AN EXTRANEOUS CATALYST; AND THEN REACTING THE THUS FORMED MONOMERIC POLYAMINOMETHYL PHENOL WITH A MEMBER SELECTED FROM THE GROUP CONSISTING OF (1) AN ACYLATION AGENT, (2) AN OXYALKYLATION AGENT, (3) AN ACYLATION THEN AN OXYALKYLATION AGENT, (4) AN OXYALKYLATION THEN AN ACYLATION AGENT, AND (5) AN ACYLATION THEN ON OXYALKYLATION AND THEN AN ACYLATION AGENT, THE PERFORMED METHYLOL PHENOL HAVING ONLY FUNCTIONAL GROUPS SELECTED FROM THE CLASS CONSISTING OF METHYLOL GROUPS AND PHENOLIC HYDROXYL GROUPS, THE POLYAMINE HAVING ONLY FUNCTIONAL GORUPS SELECTED FORM THE CLASS CONSISTING OF PRIMARY AMINO GROUPS, SECONDARY AMINO GROUPS AND HYDROXYL GROUPS, THE ACYLATION AGENT HAVING UP TO 40 CARBON ATOMS AND BEING SELECTED FORM THE CLASS CONSISTING OF UNSUBSTITUTED CARBOXYLIC ACIDS, UNSUBSTITUTED HYDROXY CARBOXYLIC ACIDS, UNSUBSTITUTED ACYLATED HYDROXY CARBOLIC ACIDS, LOWER ALKANOL ESTERS OF UNSUBSITUTED CARBOLYIC ACIDS, GYCERIDES OF UNSUBSTITUTED CARBOLYC ACIDS, UNSUBSTITUTED CARBOXYLIC ACID CHLORIDES AND UNSUBSTITUTED CARBOXYLIC ACID ANHYDRIDES, AND THE OXYALKYLATION AGENT BEING SELECTED FROM THE CLASS CONSISTING OF ALPHA-BETA ALKLENE OXIDES AND STYRENE OXIDE. 